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EP0008459A1 - Process for the production of 3-(4-methyl-3-cyclohexene-1-yl)-butyraldehyde - Google Patents

Process for the production of 3-(4-methyl-3-cyclohexene-1-yl)-butyraldehyde Download PDF

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Publication number
EP0008459A1
EP0008459A1 EP79103081A EP79103081A EP0008459A1 EP 0008459 A1 EP0008459 A1 EP 0008459A1 EP 79103081 A EP79103081 A EP 79103081A EP 79103081 A EP79103081 A EP 79103081A EP 0008459 A1 EP0008459 A1 EP 0008459A1
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Prior art keywords
rhodium
methyl
butyraldehyde
reaction
limonene
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EP79103081A
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German (de)
French (fr)
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EP0008459B1 (en
Inventor
Helmut Dr. Dipl.-Chem. Bahrmann
Boy Dr. Dipl.-Chem. Cornils
Carl Dieter Dr. Dipl.-Chem Frohning
Jürgen Dr. Dipl.-Chem. Weber
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Ruhrchemie AG
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Ruhrchemie AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Definitions

  • the present invention relates to a process for the preparation of 3- (4-methyl-3-cyclohexen-l-yl) butyraldehyde by reacting limonene with hydrogen and carbon monoxide in the presence of complex rhodium compounds as a catalyst.
  • 3- (4-Methyl-3-cyclohexen-l-yl) butyraldehyde is used as a component of perfume compositions. Its production is based on limonene, which is reacted with carbon monoxide and hydrogen in the presence of cobalt carbonyl compounds, which also contain trialkyl or triarylphosphines as ligands, or in the presence of rhodium carbonyl complexes (cf. CA Vol. 79 (197 3 ) 92400 n ).
  • the invention accordingly relates to a process for the preparation of 3- (4-methyl-3-cyclohexen-1-yl) butyr aldehyde by hydroformylation of limonene in the presence of catalysts which contain metals from group VIII of the periodic table, rhodium carbonyl complexes which additionally contain triphenyl- or trialkylphosphines as ligands being used as catalysts, and pressures of 100 to 350 bar and temperatures of 110 to 160 ° C are applied and the triphenyl- or trialkylphosphines are present in an amount of 10 to 50 mol / g atom of rhodium in the reaction mixture.
  • the use of the catalysts according to the invention ensures that the hydroformylation of limonene takes place selectively in such a way that the formyl group migrates exclusively to the terminal carbon atom of the double bond located outside the ring.
  • the rhodium catalyst is effective even in low concentrations. Usually 50 to 200 ppm of rhodium is used as the metal, based on the olefin.
  • alkylphosphine or arylphosphine is used in a large excess based on the rhodium present.
  • the use of 10 to 50 mol of phosphine / g atom of rhodium ensures that the rhodium complex always contains phosphine ligands during the reaction.
  • Suitable solvents are in particular aliphatic and aromatic hydrocarbons e.g. Hexane, octane, benzene, toluene, xylene.
  • the solvent is used in the same amount by weight as the olefin, but it is also possible to use the solvent in excess, e.g. to be used in a weight ratio of 2: 1.
  • the addition of a solvent to the reaction mixture increases the selectivity of the reaction with regard to the formation of 3- (4-methyl-3-cyclohexen-1-yl) butyraldehyde.
  • a restriction of the use of solvents can again result from economic considerations.
  • the reaction can be carried out continuously or batchwise.
  • the olefin, solvent and catalyst are placed in a suitable reactor and, after the reaction temperature has been reached, carbon monoxide and hydrogen are fed in, the gas stream being so dimensioned that the pressure selected is established.
  • the proportion of hydrogen in the carbon monoxide / hydrogen mixture is usually about 30 to 70% by volume.
  • the catalyst can be added to the reaction mixture in pre-formed form.
  • a rhodium salt for example rhodium 2-ethylhexanoate
  • the phosphine as well as form carbon monoxide and hydrogen.
  • solvent, rhodium salt and phosphine are introduced, carbon monoxide and hydrogen are added and, after the catalytically active complex has been formed, the olefin is introduced.
  • the aldehyde formed is separated off from the reaction product by distillation.
  • the catalyst remains in the distillation residue and can be returned to the reaction together with the solvent.
  • the purity of the unsaturated aldehyde, determined by gas chromatography, is 99.4%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Der als bekannter Bestandteil von Parfum-Kompositionen Anwendung findende 3-(4-Methyl- 3-cyclohexen-1-yl)- butyraldehyd der Formel <IMAGE> wird durch Hydroformylierung von Limonen der Formel <IMAGE> bei 100 - 350 bar sowie 110 - 160°C in Gegenwart von Rhodiumcarbonylkomplexen, die zusätzlich einen bestimmten Mengenbereich Triphenyl- oder Trialkylphosphine als Liganden enthalten, hergestellt.The 3- (4-methyl-3-cyclohexen-1-yl) butyraldehyde of the formula <IMAGE>, which is used as a known constituent of perfume compositions, is obtained by hydroformylation of limonene of the formula <IMAGE> at 100-350 bar and 110- 160 ° C in the presence of rhodium carbonyl complexes, which additionally contain a certain amount of triphenyl or trialkyl phosphines as ligands.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 3-(4-Methyl-3-cyclohexen-l-yl)butyraldehyd durch Umsetzung von Limonen mit Wasserstoff und Kohlenmonoxid in Gegenwart von komplexen Rhodiumverbindungen als Katalysator.The present invention relates to a process for the preparation of 3- (4-methyl-3-cyclohexen-l-yl) butyraldehyde by reacting limonene with hydrogen and carbon monoxide in the presence of complex rhodium compounds as a catalyst.

3-(4-Methyl-3-cyclohexen-l-yl)butyraldehyd findet als Bestandteil von Parfüm-Kompositionen Anwendung. Zu seiner Herstellung geht man von Limonen aus, das in Gegenwart von Cobaltcarbonylverbindungen, die neben Kohlenmonoxid zusätzlich Trialkyl- bzw. Triarylphosphine als Liganden enthalten oder in Gegenwart von Rhodiumcarbonylkomplexen mit Kohlenmonoxid und Wasserstoff umgesetzt wird (vgl. C.A. Vol. 79 (1973) 92400 n).3- (4-Methyl-3-cyclohexen-l-yl) butyraldehyde is used as a component of perfume compositions. Its production is based on limonene, which is reacted with carbon monoxide and hydrogen in the presence of cobalt carbonyl compounds, which also contain trialkyl or triarylphosphines as ligands, or in the presence of rhodium carbonyl complexes (cf. CA Vol. 79 (197 3 ) 92400 n ).

Die Selektivität dieses Verfahrens ist unbefriedigend, da der gewünschte Aldehyd nur in einer Ausbeute von 42 - 52%, bezogen auf eingesetztes Limonen gebildet wird. Aus diesem Grund ist es für eine industrielle Nutzung nicht geeignet. Es bestand daher die Aufgabe, einen Prozeß zu entwickeln, der es erlaubt, Limonen sehr selektiv und mit hoher Ausbeute in 3-(4-Methyl-3-cyclohexen-1-yl)butyraldehyd zu überführen.The selectivity of this process is unsatisfactory since the desired aldehyde is only formed in a yield of 42-52%, based on the limonene used. For this reason, it is not suitable for industrial use. The task was therefore to develop a process which allows limonene to be converted very selectively and with high yield into 3- (4-methyl-3-cyclohexen-1-yl) butyraldehyde.

Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung von 3-(4-Methyl-3-cyclohexen-1-yl)butyraldehyd durch Hydroformylierung von Limonen in Gegenwart von Katalysatoren, die Metalle der VIII. Gruppe des Periodensystems enthalten, wobei als Katalysatoren Rhodiumcarbonylkomplexe, die zusätzlich Triphenyl- oder Trialkylphosphine als Liganden enthalten eingesetzt, und Drücke von 100 bis 350 bar sowie Temperaturen von 110 bis 160°C angewendet werden und die Triphenyl- bzw. Trialkylphosphine in einer Menge von 10 bis 50 Mol/g Atom Rhodium im Reaktionsgemisch vorhanden sind.The invention accordingly relates to a process for the preparation of 3- (4-methyl-3-cyclohexen-1-yl) butyr aldehyde by hydroformylation of limonene in the presence of catalysts which contain metals from group VIII of the periodic table, rhodium carbonyl complexes which additionally contain triphenyl- or trialkylphosphines as ligands being used as catalysts, and pressures of 100 to 350 bar and temperatures of 110 to 160 ° C are applied and the triphenyl- or trialkylphosphines are present in an amount of 10 to 50 mol / g atom of rhodium in the reaction mixture.

Durch Anwendung der ausgewählten Reaktionsbedingungen können bis zu 98 % des Ausgangsstoffes in den gewünschten Aldehyd übergeführt werden.Using the selected reaction conditions, up to 98% of the starting material can be converted into the desired aldehyde.

Der Einsatz der erfindungsgemäßen Katalysatoren stellt sicher, daß die Hydroformylierung des Limonens selektiv in der Weise erfolgt, daß die Formylgruppe ausschließlich an das endständige Kohlenstoffatom der außerhalb des Ringes befindlichen Doppelbindung wandert. Der Rhodiumkatalysator ist bereits in geringer Konzentration wirksam. Üblicherweise setzt man 50 bis 200 ppm Rhodium als Metall bezogen auf das Olefin ein.The use of the catalysts according to the invention ensures that the hydroformylation of limonene takes place selectively in such a way that the formyl group migrates exclusively to the terminal carbon atom of the double bond located outside the ring. The rhodium catalyst is effective even in low concentrations. Usually 50 to 200 ppm of rhodium is used as the metal, based on the olefin.

Grundsätzlich ist es möglich, Rhodium auch in größerer Konzentration zu verwenden; man erzielt dadurch eine Erhöhung der Reaktionsgeschwindigkeit. Dem Einsatz großer Katalysatormengen steht der hohe Rhodiumpreis entgegen, der die Wirtschaftlichkeit des Verfahrens maßgeblich beeinflußt.In principle, it is possible to use rhodium in larger concentrations; an increase in the reaction rate is thereby achieved. The use of large amounts of catalyst is opposed by the high price of rhodium, which has a significant influence on the economy of the process.

Durch Einhalten eines Druckes von 100 bis 350 bar erreicht man darüber hinaus, daß die Umsetzung mit hoher Reaktionsgeschwindigkeit abläuft.By maintaining a pressure of 100 to 350 bar, it is also achieved that the reaction proceeds at a high reaction rate.

Bedeutsam für das erfindungsgemäße Verfahren ist ferner, daß das Alkylphosphin bzw. Arylphosphin in großem Überschuß bezogen auf das vorhandene Rhodium eingesetzt wird. Durch Anwendung von 10 bis 50 Mol Phosphin/g Atom Rhodium wird sichergestellt, daß der Rhodiumkomplex während der Reaktion stets Phosphinliganden enthält.It is also important for the process according to the invention that the alkylphosphine or arylphosphine is used in a large excess based on the rhodium present. The use of 10 to 50 mol of phosphine / g atom of rhodium ensures that the rhodium complex always contains phosphine ligands during the reaction.

Grundsätzlich ist es zwar möglich, die Umsetzung ohne Lösungsmittel durchzuführen, die Gegenwart eines Lösungsmittels hat sich jedoch bewährt. Geeignete Lösungsmittel sind insbesondere aliphatische und aromatische Kohlenwasserstoffe z.B. Hexan, Octan, Benzol, Toluol, Xylol. Üblicherweise setzt man das Lösungsmittel in der gleichen Gewichtsmenge wie das Olefin ein, doch ist es auch möglich, das Lösungsmittel im Überschuß, z.B. im Gewichtsverhältnis 2 : 1 zu verwenden. Der Zusatz eines Lösungsmittels zum Reaktionsgemisch erhöht die Selektivität der Umsetzung hinsichtlich der Bildung des 3-(4-Methyl-3-cyclohexen-1-yl)-butyraldehyds. Eine Beschränkung der Verwendung von Lösungsmitteln kann sich aber wiederum aus wirtschaftlichen Überlegungen ergeben.In principle, it is possible to carry out the reaction without a solvent, but the presence of a solvent has proven itself. Suitable solvents are in particular aliphatic and aromatic hydrocarbons e.g. Hexane, octane, benzene, toluene, xylene. Usually the solvent is used in the same amount by weight as the olefin, but it is also possible to use the solvent in excess, e.g. to be used in a weight ratio of 2: 1. The addition of a solvent to the reaction mixture increases the selectivity of the reaction with regard to the formation of 3- (4-methyl-3-cyclohexen-1-yl) butyraldehyde. However, a restriction of the use of solvents can again result from economic considerations.

Die Reaktion kann kontinuierlich oder diskontinuierlich durchgeführt werden. Olefin, Lösungsmittel und Katalysator werden in einem geeigneten Reaktor vorgelegt und nach Erreichen der Reaktionstemperatur Kohlenmonoxid und Wasserstoff zugeleitet, wobei der Gasstrom so bemessen wird, daß sich der gewählte Druck einstellt. Der Wasserstoffanteil im Kohlenmonoxid/Wasserstoff-Gemisch beträgt üblicherweise etwa 30 bis 70 Vol.-%. Der Katalysator kann dem Reaktionsgemisch vorgebildet zugesetzt werden.The reaction can be carried out continuously or batchwise. The olefin, solvent and catalyst are placed in a suitable reactor and, after the reaction temperature has been reached, carbon monoxide and hydrogen are fed in, the gas stream being so dimensioned that the pressure selected is established. The proportion of hydrogen in the carbon monoxide / hydrogen mixture is usually about 30 to 70% by volume. The catalyst can be added to the reaction mixture in pre-formed form.

Besonders bewährt hat es sich, den Katalysator in situ aus einem Rhodiumsalz, z.B. Rhodium-2-ethylhexanoat, dem Phosphin sowie Kohlenmonoxid und Wasserstoff zu formieren. In diesem Fall legt man Lösungsmittel, Rhodiumsalz und Phosphin vor, führt Kohlenmonoxid und Wasserstoff zu und leitet nach Bildung des katalytisch wirksamen Komplexes das Olefin ein.It has proven particularly useful to use the catalyst in situ from a rhodium salt, for example rhodium 2-ethylhexanoate, the phosphine as well as form carbon monoxide and hydrogen. In this case, solvent, rhodium salt and phosphine are introduced, carbon monoxide and hydrogen are added and, after the catalytically active complex has been formed, the olefin is introduced.

Nach Beendigung der Umsetzung wird der gebildete Aldehyd destillativ vom Reaktionsprodukt abgetrennt. Im Destillationsrückstand verbleibt der Katalysator, der zusammen mit dem Lösungsmittel in die Reaktion zurückgeführt werden kann. Es ist aber auch möglich, zunächst den Katalysator in bekannter Weise, z.B. durch Behandlung des Reaktionsgemisches mit Wasserdampf oder Wasserstoff abzutrennen und dann die Aufarbeitung des Reaktionsproduktes vorzunehmen.After the reaction has ended, the aldehyde formed is separated off from the reaction product by distillation. The catalyst remains in the distillation residue and can be returned to the reaction together with the solvent. However, it is also possible to first start the catalyst in a known manner, e.g. by treating the reaction mixture with steam or hydrogen and then working up the reaction product.

Zur weiteren Reinigung des 3-(4-Methyl-3-cyclohexen-1-yl)-butyraldehydes kann nochmals fraktioniert destilliert werden.For further purification of the 3- (4-methyl-3-cyclohexen-1-yl) butyraldehyde, fractional distillation can be carried out again.

Beispielexample

In einem Autoklaven aus rostfreiem Stahl von 4,4 1 Inhalt werden 1 1 (860 g = 6 Mol) Limonen und 1 1 (870 g = 9,5 Mol) Toluol in Gegenwart von 86 mg (= 0,8 mMol) Rhodium in Form des Rhodium-2-ethylhexanoats und 19,7 g (≙ 75 mMol) Triphenylphosphin bei 150°C und 280 bar mit einem CO/H2-Gemisch 1 : 1 umgesetzt. Nach etwa 3 Stunden, wenn keine Gasaufnahme mehr erfolgt, wird der Autoklaveninhalt auf Raumtemperatur abgekühlt. Die daran anschließende destillative Aufarbeitung des Hydroformylierungsproduktes in einer Kolonne mit 12 theoretischen Böden bei 30 Torr liefert bei einer Kopftemperatur von 35°C 875 g Toluol enthaltenden Vorlauf und bei 126°C und einer Sumpftemperatur von etwa 150°C 793 g 3-(4-Methyl-3-cycloheyen-1-yl)butyraldehyd entsprechend einer Ausbeute von 76 % bezogen auf eingesetztes Limonen.In a 4.4 liter stainless steel autoclave, 1 liter (860 g = 6 mol) limonene and 1 liter (870 g = 9.5 mol) toluene in the presence of 86 mg (= 0.8 mmol) rhodium in Form the rhodium-2-ethylhexanoate and 19.7 g (≙ 75 mmol) triphenylphosphine at 150 ° C and 280 bar with a CO / H 2 mixture 1: 1. After about 3 hours, when no more gas is taken up, the contents of the autoclave are cooled to room temperature. The subsequent distillative workup of the hydroformylation product in a column with 12 theoretical plates at 30 torr yields 875 g of toluene containing at a top temperature of 35 ° C. Lead and at 126 ° C and a bottom temperature of about 150 ° C 793 g of 3- (4-methyl-3-cycloheyen-1-yl) butyraldehyde corresponding to a yield of 76% based on the limonene used.

Die gaschromatographisch ermittelte Reinheit des ungesättigten Aldehydes liegt bei 99,4 %.The purity of the unsaturated aldehyde, determined by gas chromatography, is 99.4%.

Claims (2)

1.) Verfahren zur Herstellung von 2-(4-Methyl-3-cyclohexen-l-yl)butyraldehyd durch Hydroformylierung von Limonen in Gegenwart von Katalysatoren, die Metalle der VIII. Gruppe des Periodensystems enthalten, dadurch gekennzeichnet, daß als Katalysatoren Rhodiumcarbonylkomplexe, die zusätzlich Triphenyl- oder Trialkylphosphine als Liganden enthalten, eingesetzt und Drücke von 100 bis 350 bar sowie Temperaturen von 110 bis 160°C angewendet werden und die Triphenyl- bzw. Trialkylphosphine in einer Menge von 10 bis 50 Mol/g-Atom Rhodium im Reaktionsgemisch vorhanden sind.1.) Process for the preparation of 2- (4-methyl-3-cyclohexen-l-yl) butyraldehyde by hydroformylation of limonene in the presence of catalysts which contain metals from group VIII of the periodic table, characterized in that rhodium carbonyl complexes are used as catalysts, which additionally contain triphenyl- or trialkylphosphines as ligands, and pressures of 100 to 350 bar and temperatures of 110 to 160 ° C. are used and the triphenyl- or trialkylphosphines in an amount of 10 to 50 mol / g-atom of rhodium in the reaction mixture available. 2.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Umsetzung in Gegenwart eines Lösungsmittels, insbesondere eines aliphatischen oder aromatischen Kohlenwasserstoffes, vorgenommen wird.2.) Process according to claim 1, characterized in that the reaction is carried out in the presence of a solvent, in particular an aliphatic or aromatic hydrocarbon.
EP79103081A 1978-08-28 1979-08-22 Process for the production of 3-(4-methyl-3-cyclohexene-1-yl)-butyraldehyde Expired EP0008459B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782837480 DE2837480A1 (en) 1978-08-28 1978-08-28 METHOD FOR PRODUCING 3- (4-METHYL-3-CYCLOHEXEN-L-YL) BUTYRALDEHYDE
DE2837480 1978-08-28

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EP0008459A1 true EP0008459A1 (en) 1980-03-05
EP0008459B1 EP0008459B1 (en) 1982-04-21

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US (1) US4337363A (en)
EP (1) EP0008459B1 (en)
JP (1) JPS5533481A (en)
CA (1) CA1106857A (en)
DE (2) DE2837480A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011272A2 (en) * 1978-11-16 1980-05-28 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of aldehydes and use of the reaction products as perfumes
EP0018504A1 (en) * 1979-04-07 1980-11-12 Henkel Kommanditgesellschaft auf Aktien Use of aldehydes as microbicides
EP0052775A2 (en) * 1980-11-21 1982-06-02 L. GIVAUDAN &amp; CIE Société Anonyme Process for the production of aldehydes and intermediate products
EP0246475A2 (en) * 1986-05-13 1987-11-25 Hoechst Aktiengesellschaft Process for the preparation of aldehydes
DE102013203813A1 (en) 2013-03-06 2014-09-11 Evonik Industries Ag Oxoderivatives of limonene

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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US4471143A (en) * 1980-04-21 1984-09-11 The Franklin Institute Composition for decomposing halogenated organic compounds
DE10205835B4 (en) * 2002-02-13 2004-11-11 Celanese Chemicals Europe Gmbh Process for the preparation of terpinolenaldehyde
ATE520638T1 (en) * 2003-11-06 2011-09-15 Firmenich & Cie ALDEHYDES AS PERFUME OR FLAVOR INGREDIENTS

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US3499932A (en) * 1967-06-15 1970-03-10 Union Carbide Corp Hydroformylation of polycyclic diolefins
US3499933A (en) * 1967-06-15 1970-03-10 Union Carbide Corp Hydroformylation of cyclic olefins
DE2654799A1 (en) * 1975-12-04 1977-06-08 Kao Corp 8- AND 9-EXO-FORMYL-ENDO-TRICYCLO (5.2.1.0 HIGH 2.6) DECA-3-EN AND METHOD FOR MANUFACTURING THESE
DE2735639A1 (en) * 1976-08-09 1978-02-16 Shell Int Research CYCLOHEXANE DERIVATIVES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE
DE2753644A1 (en) * 1976-12-03 1978-06-08 Shell Int Research CYCLOPENTAN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE

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DE1939322B2 (en) * 1968-08-02 1981-02-26 Johnson, Matthey & Co., Ltd., London Process for the hydroformylation of olefinically unsaturated compounds
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US3499932A (en) * 1967-06-15 1970-03-10 Union Carbide Corp Hydroformylation of polycyclic diolefins
US3499933A (en) * 1967-06-15 1970-03-10 Union Carbide Corp Hydroformylation of cyclic olefins
DE2654799A1 (en) * 1975-12-04 1977-06-08 Kao Corp 8- AND 9-EXO-FORMYL-ENDO-TRICYCLO (5.2.1.0 HIGH 2.6) DECA-3-EN AND METHOD FOR MANUFACTURING THESE
DE2735639A1 (en) * 1976-08-09 1978-02-16 Shell Int Research CYCLOHEXANE DERIVATIVES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE
DE2753644A1 (en) * 1976-12-03 1978-06-08 Shell Int Research CYCLOPENTAN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011272A2 (en) * 1978-11-16 1980-05-28 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of aldehydes and use of the reaction products as perfumes
EP0011272A3 (en) * 1978-11-16 1980-08-20 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of aldehydes and use of the reaction products as perfumes
EP0018504A1 (en) * 1979-04-07 1980-11-12 Henkel Kommanditgesellschaft auf Aktien Use of aldehydes as microbicides
EP0052775A2 (en) * 1980-11-21 1982-06-02 L. GIVAUDAN &amp; CIE Société Anonyme Process for the production of aldehydes and intermediate products
EP0052775A3 (en) * 1980-11-21 1982-09-08 L. Givaudan & Cie Societe Anonyme Process for the production of aldehydes and intermediate products
EP0246475A2 (en) * 1986-05-13 1987-11-25 Hoechst Aktiengesellschaft Process for the preparation of aldehydes
EP0246475A3 (en) * 1986-05-13 1989-04-26 Hoechst Aktiengesellschaft Process for the preparation of aldehydes
DE102013203813A1 (en) 2013-03-06 2014-09-11 Evonik Industries Ag Oxoderivatives of limonene
WO2014135413A1 (en) 2013-03-06 2014-09-12 Evonik Industries Ag Oxo derivatives of limonene

Also Published As

Publication number Publication date
EP0008459B1 (en) 1982-04-21
DE2837480A1 (en) 1980-03-20
JPS5533481A (en) 1980-03-08
US4337363A (en) 1982-06-29
JPS5735887B2 (en) 1982-07-31
DE2962566D1 (en) 1982-06-03
CA1106857A (en) 1981-08-11

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